Fibers, a process for preparing the same and product thereof

ABSTRACT

PCT No. PCT/JP95/01901 Sec. 371 Date Apr. 16, 1997 Sec. 102(e) Date Apr. 16, 1997 PCT Filed Sep. 21, 1995 PCT Pub. No. WO97/67279 PCT Pub. Date Feb. 27, 1997The present invention relates to cellulose fibers excellent in dirt removability and a method of treatment thereof. The cellulose fibers of the invention are liquid ammonia-treated cellulose fibers whose partial or entire exterior is coated with an ester of (A) a polycarboxylic acid having at least three carboxyl groups and (B) a hydrophilic polyol having an oxyethylene group or groups and at least two alcoholic hydroxyl groups and/or which fibers are impregnated with the ester.

This application is a 371 of PCT/JP95/01901 filed Sep. 21, 1995.

FIELD OF THE INVENTION

The present invention relates to cellulose fibers excellent in theproperty of removing dirt, a process for preparing the same and aproduct thereof. The invention also concerns with a product ofcellulose-free synthetic fibers and a process for preparing the productthereof.

BACKGROUND ART

Cellulose fibers, typically cotton, are widely used for clothes andproducts of fibers because of their many advantages such as highhygroscopicity and good feel. Products of cellulose fibers are soiledwith oil, sebum, mud or the like due to the use and wearing and arecleaned by laundry for re-use. However, such dirt is likely to cling tocellulose fibers and products thereof and can not be easily removed bylaundry. Consequently, this leads to disadvantages of stain, blacksmear, discolored smudge, etc. which reduce the value of clothes and thelike. For this reason, a need exists for products of cellulose fibershaving improved dirt-removing property (dirt removability). Dirt doesnot easily come off by laundry from cotton and the like which readilyabsorb oily and aqueous substances. So far, products of cotton free fromsaid problem have not been found.

In such current situation, it has been proposed to attach polyvinylalcohol as a laundry size to products of cellulose fibers. The proposedmethod contemplates causing the dirt to adhere to polyvinyl alcohol sothat the dirt is separated, together with polyvinyl alcohol, from theproduct of cellulose fibers by laundry. However, the method can achievethis effect only once, and necessitates depositing polyvinyl alcohol ona product of cellulose fibers every time the product is washed. Thus themethod can not be said to be means for improving dirt removability.

On the other hand, polyester, nylon and other synthetic fibers areextensively used for their numerous advantages such as high mechanicalproperties, chemical resistance and ease of care, but have a drawback oftending to permit accumulation of static electricity. Various antistaticagents have been used to overcome the drawback, but substantially all ofthem come off during laundry and are merely temporarily effective.

For practical use as clothes, products of synthetic fibers should beimparted laundry durability as well as antistatic property. As a methodof giving antistatic property to a product of synthetic fibers, it isknown to coat synthetic fibers with a hydrophilic polymer having doublebonds by radical polymerization (Japanese Examined Patent PublicationNo.40,554/1985).

However, a fully crosslinked polymer needs to be formed to produce acoating film having the required washing resistance from a hydrophilicpolymer. The radical polymerization of a hydrophilic polymer with doublebonds for conversion to a crosslinked polymer entails a disadvantage ofessentially using an ethyleneimine derivative, i.e. a highly toxiccrosslinking agent or a volatile, highly toxic acrylic acid.

Said conventional procedure makes it difficult to maintain hygiene andhealthy working environment, and needs special apparatus. Therefore theprocedure has not been a useful technique in an ordinary processingplant which is intended to use mainly open-type equipment. Further aserious problem has been posed in that products of synthetic fibersshould be subjected to a washing process of considerable scale to makethe product of synthetic fibers non-skin irritable.

The accumulation of static electricity described above is due to theinherent hydrophobicity of synthetic fiber resins. The hydrophobicity ofsynthetic fiber resins raises another disadvantage that dirt is firmlyheld by products of synthetic fibers. In other words, dirt, for example,oily dirt such as oil grime and lipstick smudge is not easily removedfrom clothes of synthetic fibers and will not easily come off bywashing. Unavoidably the dirt remains on products of synthetic fibers.However, no technique has been developed to improve the dirtremovability of synthetic fiber products and to prevent dirt frompermanently sticking to synthetic fiber products.

DISCLOSURE OF THE INVENTION

A first object of the present invention is to provide cellulose fiberswhich are excellent in the dirt removability and which are free fromimpairment of properties due to repeated laundry, a process forpreparing the cellulose fibers and a product thereof.

A second object of the invention is to provide a product of syntheticfibers which are excellent in the antistatic property and the dirtremovability, and a technique for preparing said product of syntheticfibers with safety and ease.

Other features of the present invention will become apparent from thefollowing description.

According to the present invention, there are provided liquidammonia-treated cellulose fibers whose partial or entire exterior iscoated with an ester of (A) a polycarboxylic acid having at least threecarboxyl groups and (B) a hydrophilic polyol having an oxyethylene groupor groups and at least two alcoholic hydroxyl groups and/or which fibersare impregnated with said ester.

The cellulose fibers of the present invention can be prepared by aprocess comprising the steps of treating cellulose fibers with liquidammonia, depositing an ester of (A) a polycarboxylic acid having atleast three carboxyl groups (hereinafter referred to as "presentpolycarboxylic acid") and (B) a hydrophilic polyol having an oxyethylenegroup or groups and at least two alcoholic hydroxyl groups (hereinafterreferred to as "present polyol") on partial or entire exterior of liquidammonia-treated cellulose fibers and/or impregnating the fibers withsaid ester, or by a process comprising the steps of depositing thepresent polycarboxylic acid and the present polyol on partial or entireexterior of liquid ammonia-treated cellulose fibers, and/or impregnatingthe fibers with the present polycarboxylic acid and the present polyol,and heating the fibers (these steps being hereinafter called"esterification treatment").

A product of cellulose fibers according to the present invention can beprepared by (1) treating the cellulose fibers with liquid ammonia,subjecting the fibers to esterification treatment and making the fibersinto a product thereof by a conventional method or (2) treating thecellulose fibers with liquid ammonia, making the fibers into a productthereof by a conventional method and subjecting the product toesterification treatment.

The cellulose fibers of the invention and a product thereof areoutstanding in the dirt removability and the property of maintaining thedirt removability without impairment even on exposure to repeatedlaundry (hereinafter called "laundry durability"). Dirt is unlikely tocling to the cellulose fibers of the present invention and productsthereof. Examples of dirt are oily dirt derived from motor oil, machineoil, grease, lipstick, edible-oil, shoe polish, wax, sebum (so-calleddirt on the collar), and aqueous dirt derived from mud, Indian ink,carbon (pencil), foods, seasonings (soy sauce, Worcester sauce, ketchup,curry, sauce for roast meat, etc.), and beverages (green tea, coffee,etc.). Even if dirt should come to lie on the cellulose fibers of theinvention, the dirt would be scarcely likely to adhere to the fibers dueto the remarkable dirt removability of the fibers.

According to the invention, there is also provided a product ofsynthetic fibers coated with an ester of (A) the present polycarboxylicacid and (B) the present polyol.

The products of synthetic fibers according to the invention have a highantistatic property and a good laundry durability and are substantiallyfree from the reduction of antistatic property even when exposed torepeated washing. Dirt is unlikely to stick to the products of syntheticfibers according to the invention, examples of dirt being oily dirtderived from motor oil, machine oil, grease, lipstick, edible oil, shoepolish, wax, sebum (so-called dirt on the collar), and aqueous dirtderived from mud, Indian ink, carbon (pencil), foods, seasonings (soysauce, Worcester sauce, ketchup, curry, sauce for roast meat, etc.), andbeverages (green tea, coffee, etc.). Even if dirt should come to lie onthe synthetic fiber products of the invention, the dirt would scarcelytend to cling to the products due to the outstanding dirt removabilityof the fibers. The products of synthetic fibers according to theinvention are excellent in the water-absorbing capacity and have a goodfeel of course when the products are produced by mix-spinning syntheticfibers and cellulose fibers or even when the products are producedwithout using cellulose fibers.

According to the processes of the present invention, the desiredcellulose fibers, products of cellulose fibers and products of syntheticfibers can be prepared with safety and ease.

Further, the present polycarboxylic acid and the present polyol to beused in the present invention are non-toxic and non-volatile andtherefore are free from problems of hygiene and working environments.

Discussed below are the improved cellulose fibers of the presentinvention, processes for preparing the same and products of cellulosefibers.

The term "cellulose fibers" used herein refers to natural cellulosefibers such as cotton and hemp, regenerated cellulose fibers such asrayon, and fibers produced by mix-spinning these fibers. The cellulosefibers of the present invention include not only the foregoing fibersbut those made by primary processing of these fibers such as threads,knit, textile, knitting, non-woven fabric, etc. The term "product ofcellulose fibers according to the invention" used herein means productsproduced by further processing the foregoing cellulose fibers such asclothes, beddings, interior goods, etc.

In the practice of the invention, the cellulose fibers of the inventionor products thereof can be mix-spun, twisted or knitted together withthe cellulose-free synthetic fibers.

Examples of cellulose-free synthetic fibers include a wide variety ofthose heretofore known, such as the synthetic fibers made of polyester,liquid crystal polyester, polyamide, liquid crystal polyamide, acryl,polyethylene, polypropylene, Spandex or the like. Among said syntheticfibers, those of polyester, polyamide, acryl or polypropylene arepreferred and those of polyester are more preferred.

In mix-spinning the cellulose fibers and said synthetic fibers, themix-spinning ratio is not specifically limited, but the synthetic fibersmay be used in a ratio of up to 80% by weight, preferably up to 70% byweight, based on the total fibers.

For treating the cellulose fibers with liquid ammonia according to theinvention, a wide variety of conventional methods can be used andinclude, for example, the method disclosed in Japanese Unexamined PatentPublication No.152,595/1977, "Why Cotton ?", Commodity Knowledge ofCotton Products (published by Japanese Cotton Industry PromotionAssociation, 1994), etc.

For example, the liquid ammonia-treated cellulose fibers to be used inthe invention can be prepared by immersing cellulose fibers in liquidammonia to swell the fibers and removing ammonia from the swollenfibers. Swelling occurs by immersion of fibers in liquid ammonia for 0.1to 200 seconds, preferably 5 to 30 seconds. The removal of ammonia canbe done by any of dry steam method and water method.

According to the dry steam method, liquid ammonia is vaporized forremoval by contact of the fibers with a high speed roller in treatingthe fibers with liquid ammonia. In the practice of the invention, amethod can be used which comprises accelerating the removal of ammoniaby water vapor or a thin layer of water after contact with a high speedroller. The water method comprises removing ammonia using water as amedium after treatment with liquid ammonia. Stated more specifically,the method comprises washing the fibers with low temperature water andthen with warm water and drying them by a high temperature cylinder.

The cellulose fibers of the invention are subjected to esterificationtreatment after treatment with liquid ammonia. The esterificationtreatment is described below in detail.

Examples of the present polycarboxylic acid for use in the inventioninclude a wide range of conventional polycarboxylic acids which have atleast 3 carboxyl groups, such as aliphatic polycarboxylic acids,alicyclic polycarboxylic acids, aromatic polycarboxylic acids, etc.These polycarboxylic acids may have a hydroxyl group, halogen group,carbonyl group and carbon-carbon double bonds.

More specific examples of the present polycarboxylic acids are tribasicacids such as tricarballylic acid, aconitic acid, methylcyclohexenetricarboxylic acid and citric acid, tetrabasic acids such asbutanetetracarboxylic acid, cyclopentanetetracarboxylic acid,tetrahydrofurantetracarboxylic acid and an ene adduct of methyltetrahydrophthalate with maleic acid, trimellitic acid, pyromelliticacid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid,diphenylsulfonetetracarboxylic acid and like aromatic polycarboxylicacids, tetracarboxylic acids prepared from styrene and maleic anhydrideby Diels-Alder reaction and ene reaction, etc. These polycarboxylicacids can be used either alone or in combination. Among thesepolycarboxylic acids, water-soluble polycarboxylic acids such astricarballylic acid, aconitic acid and citric acid are preferred becauseof high workability. Butane-tetracarboxylic acid which is water-solubletetrabasic acid can achieve the highest effect and hence is morepreferred.

The present polyols to be used in the invention include a wide varietyof conventional polyols which have an oxyethylene group (or groups) andat least 2 alcoholic hydroxyl groups. Specific examples are polyethyleneoxide, polypropylene oxide, adducts of ethylene oxide with compoundshaving at least 2 active hydrogen atoms such as amines, phenols,alcohols or the like. These polyols can be used either alone or incombination.

Examples of compounds having at least 2 active hydrogen atoms which canbe used in the invention are neopentyl glycol, methylpentanediol,trimethylpentanediol and like diols having 5 to 12 carbon atoms andtheir branched alcohols; polypropylene glycol, polymers of 1,2-butyleneoxide, poly(1,4-butylene glycol) and like polyether alcohols; glycerin,diglycerin, triglycerin, polyglycerin, trimethylolethane,trimethylolpropane, pentaerythritol, dipentaerythritol and like alcoholshaving at least 3 hydroxyl groups; cyclohexanediol,cyclohexanedimethanol, hydrogenated bisphenol A, spiroglycol,geometrical isomers thereof and like alicyclic alcohols; xylitol,sorbitol, mannitol, erythritol and like reducing sugars; xylose,sorbose, arabinose, ribose, erythrose, galactose, sorbitan and likemonosaccharides; lactose, sucrose, maltose and like disaccharides;hydroquinone, resorcin, catechol, bisphenol A, bisphenol S, phenolnovolak, cresol novolak and like phenols; ammonia, monoalkylamine having1 to 22 carbon atoms, alkylenediamine, alkylenetriamine, aniline, o-,m-, p-phenylenediamine, xylylenediamine, diaminodiphenylmethane,diaminodiphenylsulfone, diaminodiphenyl ether, diaminodiphenyl ketoneand polycondensate of aniline and formalin.

Polyethylene glycol and adducts of ethylene oxide such as bisphenol A,pentaerythritol, ethylenediamine or the like are the most preferredbecause of their effects, workability, availability of raw materials andgood feel of finished products.

Polyester polyols prepared from said polyols and aliphatic dicarboxylicacid having 2 to 12 carbon atoms or aromatic dicarboxylic acid can beused as the present polyol. Among these polyester polyols, those atleast soluble in a solvent, preferably in water are desirable. Thepolyols which can be emulsified or solubilized with a surfactantalthough insoluble in water can be used.

The present polyol preferably has a molecular weight of 200 to 20,000.Even a polyol having a molecular weight of less than 200 can bepreferably used in the present invention when mixed with a polyol morethan 200 in molecular weight to give mixed polyols with an averagemolecular weight within said range. Even a polyol having a molecularweight of more than 20,000 can be preferably used in the presentinvention when mixed with a polyol less than 20,000 in molecular weightto give mixed polyols having an average molecular weight within saidrange. Further in the present invention, the present polyol can be usedas mixed with a compound containing said active hydrogen atoms as suchor as mixed with an adduct of a small number of moles of ethylene oxidewith said compound having a molecular weight of less than 200. Thepresent polyol 400 to 2,000 in molecular weight is more preferred.

The ester to be deposited on and/or diffused into the liquidammonia-treated cellulose fibers is an ester of the presentpolycarboxylic acid and the present polyol which has at least twocarboxyl groups in one molecule. Typical examples of the structure ofsuch polyester are as follows.

    (A.sub.1)-- (B)--(A.sub.2)!.sub.1 --(B)--(A.sub.1)         (1)

    (B)-- (A.sub.2)--(B)!.sub.m --(A.sub.2)--B                 (2)

    (A.sub.1)-- (B)--(A.sub.2)!.sub.n --B                      (3)

wherein A₁ is a terminal group derived from the present polycarboxylicacid; when the present polycarboxylic acid is tricarboxylic acid, it is(HO₂ C)₂ (R)CO₂ -- and when it is tetracarboxylic acid, it is (HO₂ C)₃(R)CO₂ -- wherein R is a polycarboxylic acid residue, A₂ is a diestergroup derived from the present polycarboxylic acid, B is a residuederived from the present polyol, and l, m and n are integers of 0 to500.

The ester to be used in the present invention is preferably awater-soluble ester from the viewpoints of the properties andworkability. The most preferred among such esters is an ester ofpolyethylene glycol with 1,2,3,4-butanetetracarboxylic acid, that is,the ester having the structure as shown below in the foregoing formulas(1) to (3). ##STR1## wherein o is an integer of 5 to 500.

Said ester can be prepared by dehydration esterification of the presentpolycarboxylic acid and the present polyol. As to the proportions of thepresent polycarboxylic acid and the present polyol used in thepreparation of the ester, 0.01 to 20 moles, preferably 0.25 to 4 moles,more preferably 0.5 to 1 mole, of the present polycarboxylic acid, permole of alcoholic hydroxyl group of the polyol. The esterification maybe conducted in the absence of a solvent or in the presence of a knowncatalyst. It is preferred not to use a solvent from the standpoint ofthe workability. The catalyst to be optionally used is preferably thesame substance as a neutralizing agent described later and incorporatedinto a treating solution in use for depositing the ester on, and/ordiffusing the ester into, the liquid ammonia-treated cellulose fibers.The dehydration esterification can be carried out by mixing the twocomponents, heating them to about 80 to about 200° C. and optionallydistilling off the produced water. The reaction pressure in thedehydration esterification may be atmospheric pressure or reducedpressure.

In the present invention, the ester described above is deposited on partor the entire area of the surface of the liquid ammonia-treatedcellulose fibers and/or diffused into the fibers. The amount of theester deposited and/or internally diffused is variable depending on thetype of the ester or other factors and indeterminable, but is 0.01 to30% by weight, preferably 1 to 20% by weight, based on the liquidammonia-treated cellulose fibers. A high dirt removability is exhibitedwhen the amount of the ester used is in this range.

In depositing the ester on partial or entire exterior of the liquidammonia-treated cellulose fibers and/or diffusing the ester into thefibers, the present polycarboxylic acid is preferably used incombination with the ester depending on the molar ratio of the presentpolycarboxylic acid and the present polyol composing the ester.Especially it is recommendable to add the present polycarboxylic acid incombination with the ester when less than 0.5 mole of the presentpolycarboxylic acid is employed per mole of the alcoholic hydroxyl groupof the present polyol. The present polycarboxylic acid may be added incombination even when more than 0.5 mole is used per mole of thealcoholic hydroxyl group of the present polyol.

According to the present invention, the present polycarboxylic acid andthe present polyol constituting the ester may be individually depositedon and/or diffused into the liquid ammonia-treated cellulose fibers,instead of depositing the ester on and/or diffusing the ester into theliquid ammonia-treated cellulose fibers. As to the proportions of thepresent polycarboxylic acid and the present polyol separately used inthis case, 0.01 to 20 moles, preferably 0.25 to 4 moles, more preferably0.5 to 1 mole, of the present polycarboxylic acid is used per mole ofalcoholic hydroxyl group of the polyol. The amount of the presentpolycarboxylic acid deposited and/or internally diffused is variabledepending on the type of the present polycarboxylic acid or otherfactors and indeterminable, but is 0.01 to 20% by weight, preferably 0.1to 10% by weight, based on the liquid ammonia-treated cellulose fibersto be processed. The amount of the present polyol deposited and/orinternally diffused is variable depending on the type of the presentpolyol or other factors and indeterminable, but is 0.1 to 30% by weight,preferably 1 to 20% by weight, based on the liquid ammonia-treatedcellulose fibers to be processed. A high dirt removability is exhibitedwhen the amount of each of the two components deposited and/orinternally diffused is in this range.

In the practice of the present invention, a conventional fiber-softeningagent as well as said components may be deposited on and/or diffusedinto the cellulose fibers. For example, if a polyethylene emulsion or afiber-softening silicone is deposited on the cellulose fibers orproducts thereof, an improved feel and enhanced persistence would beimparted to the cellulose fibers or products thereof.

Fiber-softening silicones are compounds having, as a basic skeleton,dimethylpolysiloxane containing at least one aliphatic hydroxyl groupand/or amino group and/or carboxyl group in the molecule. Preferredsilicones are so-called amino-modified silicone, polyether-modifiedsilicone, epoxy-modified silicone and carboxyl-modified silicone.

An amino-modified silicone may color treated cellulose fibers orproducts thereof depending on the type or amount of the silicone. Apolyether-modified silicone, epoxy-modified silicone andcarboxyl-modified silicone are preferable. These silicones are availablein the form of the solid as produced, an emulsion or an aqueous siliconeand can be used as such.

The amount of the fiber-softening agent deposited and/or internallydiffused is 0.01 to 50% by weight, preferably 0.1 to 10% by weight,based on the product of cellulose fibers to be processed.

The ester or the present polycarboxylic acid, the present polyol and thelike may be deposited on and/or diffused into the cellulose fibers byvarious conventional methods such as dipping, spraying, coating and thelike. In the practice of the invention, the so-called dipping techniqueis preferred in which the cellulose fibers to be treated are dipped intoa treating solution containing the ester or the present polycarboxylicacid, the present polyol, etc. The dipping technique is described belowin detail.

The concentration of the ester or the concentrations of the presentpolycarboxylic acid and the present polyol in the treating solution canbe determined by calculation from the squeezing ratio of the treatingsolution and the amount of the treating solution required to be carried.

It is suitable to adjust the treating solution to a pH of 0 to 6,preferably 2 to 5. If the treating solution has a pH in said range, thecellulose fibers would be given higher dirt removability and enhancedlaundry durability. The pH range of the treating solution can beadjusted by adding a neutralizing agent, namely a suitable alkali orsalt, to the treating solution.

Examples of the neutralizing agent to be used for the adjustment of a pHare sodium hydroxide, sodium bicarbonate, sodium carbonate, sodiumpercarbonate, sodium borate, sodium metaborate, sodium borohydride,sodium silicate, sodium metasilicate, sodium sulfate, sodium sulfite,sodium thiosulfate, sodium phosphate, sodium metaphosphate, sodiumpolyphosphate, sodium pyrophosphate, sodium phosphite, sodiumhypophosphite, sodium formate, sodium acetate, sodium malate, sodiumtartrate and sodium lactate. Salts of potassium, salts of ammonium, andsalts of methylamine, dimethylamine, trimethylamine, triethylamine orlike volatile lower amines can be used in place of said sodium salts.These neutralizing agents can be used either alone or in combination.

The amount of the neutralizing agent used is variable depending on thetype and the dissolution amount of the ester or the presentpolycarboxylic acid but is about 0.1 to about 10% by weight, calculatedas the concentration in the treating solution.

The solvent constituting the treating solution may be an organic solventbut preferably is water from the viewpoints of safety and costs. Theform of the treating solution is not specifically limited insoafar asthe desired effect can be achieved. A suitable form may be a solution oran emulsion. An aqueous solution is preferred from the viewpoints oftreating efficiency and safety.

The liquid ammonia-treated cellulose fibers are dipped in the treatingsolution prepared above to deposit the ester or the presentpolycarboxylic acid, the present polyol and like components on thefibers and/or to diffuse them into the fibers and then usually thefibers are heated after squeezing, whereby the cellulose fibers of thepresent invention are produced.

Since the treating solution can be deposited on or diffused into thefibers at a sufficiently high rate, the dipping time and the bathtemperature are not specifically limited. Usually the dipping time is0.1 to 300 seconds, and the bath temperature is 10° to 40° C. Squeezingmethods are different depending on the product to be processed, and asuitable method and a proper squeezing ratio can be selected. Usually apreferred squeezing ratio is 30 to 200%.

The cellulose fibers are dried after dipping and squeezing. The dryingtemperature is 40° to 150° C. and the drying time is selected accordingto the temperature.

In the invention, subsequently there are heat-treated the cellulosefibers externally or internally having the ester or the presentpolycarboxylic acid, the present polyol and other components. The heattreatment causes esterification reaction of the present polycarboxylicacid and the present polyol sticking to the fibers for conversion intoan ester, and not only the surface of the fibers is partly or completelycoated with the ester, but also a reaction occurs between the carboxylgroup of the present polycarboxylic acid and the hydroxyl group of thecellulose fibers to give a firm coating film of the reaction productchemically bonded to the exterior and/or the interior of individualfibers. When the ester prepared by the esterification of the presentpolycarboxylic acid and present polyol is used, the same coating film isformed. If other components than the present polycarboxylic acid andpresent polyol or the ester, such as a fiber-softening silicone, aredeposited on and/or diffused into the fibers, the components are reactedby heat treatment together with the present polycarboxylic acid and thepresent polyol or the ester to produce a reaction product as saidcoating film.

The heat-treating temperature is 100° to 250° C., preferably 120° to200° C. The heat-treating time is 20 seconds to 1 hour. The heattreatment under these conditions provides the cellulose fibers of thepresent invention with improved dirt removability and enhanced laundrydurability.

The cellulose 1086Xfibers processed are subjected to further treatmentssuch as washing with water, soaping and addition of fiber-softeningagent and others to give the desired product of cellulose fibers. If theproduct of cellulose fibers is a thread, the thread is made intotextile, knit, non-woven fabric or the like by conventional methods, andthese products are processed into clothes, interior goods, bedding orother end products.

Examples of products of cellulose fibers according to the presentinvention are outer clothing, intermediate clothing and under clothing.More specific examples are jackets, trousers, skirts, shirts, blouses,nightwears, underwears, stockings, aprons, polo shirts, white robes,gloves, etc. Further examples are embroidery threads, machine cotton,gauzes, flu masks, handkerchiefs, cotton for bedding, pot-holding pads,sneakers, linings and insoles for shoes, towels, dishcloths, covers forarmchairs, outer cloth materials for chairs, cushions, bedding covers,blankets made of cotton, blankets made of toweling, etc.

In the present invention, the cellulose fibers are, as described above,treated with liquid ammonia, subjected to esterification treatment andare made into a product of cellulose fibers by conventional methods. Theproduct of cellulose fibers according to the invention can be producedalso by the following processes.

A process is employable which comprises treating the cellulose fiberswith liquid ammonia, making the liquid ammonia-treated cellulose fibersinto a product thereof, depositing the ester of the presentpolycarboxylic acid and the present polyol on partial or entire exteriorof cellulose fibers and/or diffusing the ester into the fibers, andfinally heating the fibers, whereby a product thereof is produced.Another process employable comprises treating the cellulose fibers withliquid ammonia, making the liquid ammonia-treated cellulose fibers intoa product thereof, depositing the present polycarboxylic acid and thepresent polyol on partial or entire exterior of cellulose fibers and/ordiffusing them into the fibers, and finally heating the fibers, wherebya product thereof is produced. The conditions for the liquid ammoniatreatment, deposition or diffusion of the ester or the presentpolycarboxylic acid and present polyol and heat treatment are the sameconditions as described hereinbefore for the cellulose fibers.

Next, the product of cellulose-free synthetic fibers according to theinvention and a process for preparing the product are described below.

Products of synthetic fibers according to the invention include, forexample, filaments made of cellulose-free synthetic fibers or made bymix-spinning said synthetic fibers and cellulose fibers, processedproducts of said filaments, such as threads, textile, knit, non-wovenfabric, clothes, curtains, etc.

The cellulose-free synthetic fibers and the cellulose fibers are asdescribed above. The cellulose fibers to be used herein are thoseuntreated with ammonia. Preferred examples of said synthetic fibers arefibers made of polyester, polyamide, acryl or polypropylene. Among them,fibers of polyester are more preferred. Of said cellulose fibers, cottonis favorable. In the case of mixed fibers made by mix-spinning thesynthetic fibers and the cellulose fibers, the mix-spinning ratio issuitably selected from the range in which the properties of thesynthetic fibers are not impaired. It is desirable that the mixed fiberscontain the cellulose fibers in an amount of less than 80% by weight,preferably less than 70% by weight, most preferably less than 50% byweight, based on the total fibers.

The product of synthetic fibers according to the invention can beproduced by depositing the present polycarboxylic acid and the presentpolyol on the synthetic fibers and heat-treating the fibers.

The amount of the present polycarboxylic acid deposited on the productof synthetic fibers can be suitably selected over a wide range dependingon its type, but is 0.01 to 20% by weight, preferably 0.1 to 10% byweight, based on the synthetic fiber product to be processed. If theamount of the present polycarboxylic acid deposited is below the range,the synthetic fiber product tends to achieve lower effects than ascontemplated in the invention, e.g. reduced antistatic effect and dirtremovability, whereas a more amount are unlikely to produce effectscorresponding to the amount, and hence it is uneconomical.

The amount of the present polyol deposited on the product of syntheticfibers is 0.1 to 30% by weight, preferably 1 to 20% by weight, based onthe synthetic fiber product to be processed. If the amount of the polyoldeposited is below the range, the synthetic fiber product tends to showdecreased antistatic effect and dirt removability, whereas a more amountis unlikely to produce effects corresponding to the amount and hence itis uneconomical.

According to the present invention, at least one compound selected fromcompounds represented by the formula (4) shown below and cationiccelluloses is preferably deposited on the product of synthetic fiberstogether with the present polycarboxylic acid and the present polyol:

    Xa--A--Yb                                                  (4)

wherein A is an aliphatic hydrocarbon group, an aromatic hydrocarbongroup, an oxyalkylene group having 2 to 4 carbon atoms or apoly(polymerization degree: 2 to 20)oxyalkylene group, X is an alcoholichydroxyl group, or an amino group, Y is --SO₃ M group, --OSO₃ M group,--N(R¹)(R²) group or --N⁺ (R³)(R⁴ )(R⁵)·X⁻ in which M is a hydrogenatom, an alkali metal atom, an ammonium base, an alkylamine base or analkanolamine base, X⁻ is a halogen ion, a perchloric acid ion, analkylsulfonic acid ion or an alkyl arylsulfonic acid ion, R¹, R², R³, R⁴and R⁵ are the same or different and each represents a hydrogen atom, analiphatic group of 1 to 22 carbon atoms or an aromatic group, both ofthe aliphatic group and the aromatic group optionally having an amidegroup or an oxyalkylene group, a and b are integers of 1 to 3, providedthat when A is an oxyalkylene group of 2 carbon atoms and X is analcoholic hydroxyl group, a must not be 2 or 3 and provided that thecompound wherein R¹ and R² are both hydrogen atoms and the compoundwherein R³, R⁴ and R⁵ are all hydrogen atoms are excluded. Thedeposition of the compound(s) increases the effect as contemplated bythe invention.

The compounds of the formula (4) which can be used include a widevariety of conventional compounds which have at least one amino groupand/or an alcoholic hydroxyl group. Specific examples are compoundswhich pertain to the groups described below.

(1) Sulfonic acids containing at least one amino group and/or alcoholichydroxyl group and salts thereof

Examples of the compounds in this group are isethionic acid,aminobenzenesulfonic acid, aminonaphthalenesulfonic acid, adducts ofthese acids with alkylene oxide of 2 to 4 carbon atoms, and alkali metalsalts or amine salts of adducts of phenolsulfonic acid, naphtholsulfonicacid or the like with alkylene oxide of 2 to 4 carbon atoms. Among them,it is preferred to use isethionic acid or an adduct of said acid withethylene oxide, and salts of alkali metals with an adduct ofphenolsulfonic acid with ethylene oxide in order to provide theprocessed cloth capable of maintaining white color.

(2) Amines having at least one amino group and/or alcoholic hydroxylgroup

The amine is represented by the formula (5) or (6) ##STR2## wherein R⁶is an alkyl group of 1 to 22 carbon atoms or an alkenyl group of 1 to 22carbon atoms, both of the alkyl group and the alkenyl group optionallyhaving an amide group or an oxyalkylene group of 2 to 4 carbon atoms, A'is an oxyalkylene group of 2 to 3 carbon atoms, and c and d are integersof at least 1, and c+d is an integer of at least 2, preferably 2 to 20,and ##STR3## wherein R⁷ and R⁸ are the same or different, and eachrepresents a hydrogen atom, an alkyl group of 1 to 22 carbon atoms or analkenyl group of 1 to 22 carbon atoms, both of the alkyl group and thealkenyl group optionally having an amide group or an oxyalkylene groupof 2 to 4 carbon atoms, provided that R⁷ and R⁸ together can not behydrogen atoms, A' is as defined above, and e is an integer of at leastone, preferably an integer of 1 to 20.

(3) Ammonium salts containing at least one amino group and/or alcoholichydroxyl group

The compound is represented by the formula (7) or (8) ##STR4## whereinR⁹ and R¹⁰ are the same or different, and each represents a hydrogenatom, an alkyl group of 1 to 22 carbon atoms or an alkenyl group of 1 to22 carbon atoms, both of the alkyl group and the alkenyl groupoptionally having an amide group or an oxyalkylene group of 2 to 4carbon atoms, provided that R⁹ and R¹⁰ together can not be hydrogenatoms, A' is as defined above, X is a halogen ion (such as Cl, Br or I),a perchloric acid ion, an alkylsulfonic acid ion (such as monomethylsulfate residue), or an alkyl arylsulfonic acid ion (such asdodecylbenzene-sulfonic acid ion), f and g are integers of at least 1,and f+g are an integer of at least 2, preferably 2 to 20, and ##STR5##wherein R¹¹, R¹² and R¹³ are the same or different, and each representsa hydrogen atom, an alkyl group of 1 to 22 carbon atoms or an alkenylgroup of 1 to 22 carbon atoms, both of the alkyl group and the alkenylgroup optionally having an amide group or an oxyalkylene group of 2 to 4carbon atoms, provided that R¹¹, R¹² and R¹³ together can not behydrogen atoms, A' and X are as defined above, and h is an integer of atleast 1, preferably 1 to 20.

To avoid the yellowing of the processed fiber product, tertiary amine ispreferred among these amines. Of ammonium salts, quaternary ammoniumsalt is preferable. Quaternary ammonium salt is the most preferredbecause it is excellent in the antistatic effect and dirt removability.It is desirable that these amines or ammonium salts be soluble in wateror be in a stably emulsified state in the treating solution wherein thepresent polycarboxylic acid and the present polyol are dissolved. Eventhe amines and ammonium salts which can not be emulsified by themselvescan be used if they are made emulsifiable by the addition of asurfactant.

Useful cationic celluloses include, for example, O-2-hydroxy-3-(trimethylammonio)propyl!-hydroxyethyl cellulose chloride.

The amount of the compound of the formula (4) and/or the cationiccellulose deposited is 0.01 to 100 mole %, preferably 0.1 to 20 mole %,based on the present polycarboxylic acid.

In the practice of the invention, the antistatic effect of the syntheticfiber product according to the present invention can be markedlyincreased by depositing a conventional antistatic agent on the product.

Examples of antistatic agents to be used are anionic surfactants such asthose prepared from alkyl sulfate, alkyl amidosulfate, alkyl sulfonate,alkyl amidosulfonate, alkyl ether sulfonate, alkyl arylsulfonate, alkylphosphite, alkyl phosphate and the like, cationic surfactants such ashydrocarbonate, hydrochloride, perchlorate, acetate, citrate,alkylpyridinium salt, alkylamidopyridinium salt, alkyl ether pyridiniumsalts or the like, e.g. those from alkyl amidoamine, alkyltrimethyl,alkyldimethylbenzyl, alkylamide, quaternary ammonium salt,alkyloxazoline, alkylimidazoline, aminoethylimidazoline, dihydroindole,alkylaminotriazole, alkyldioxane and the like, and amphotericsurfactants such as those from betaine, imidozoline, sulfate, sulfonicacid, phosphate and the like.

In the practice of the invention, a conventional fiber-softening agentas well as said components may be deposited on the product of syntheticfibers. For example, if a polyethylene emulsion or a fiber-softeningsilicone is deposited on the product of synthetic fibers, an improvedfeel and enhanced persistence would be imparted to the product ofsynthetic fibers.

The fiber-softening silicones are compounds having, as a basic skeleton,dimethylpolysiloxane containing at least one aliphatic hydroxyl groupand/or amino group in the molecule. These silicones are generally calledamino-modified silicone (formula (9)), or polyether-modified silicone(formula (10)) and are commercially available. ##STR6##

An amino-modified silicone may color the treated fiber product dependingon the type or amount of the silicone. A polyether-modified silicone ispreferred to such silicone. An epoxy-modified silicone is producedsubstantially via an aliphatic hydroxyl group and thus is included insaid fiber-softening silicones. These silicones are available in theform of the solid as produced or an emulsion, and can be used as such.

The amount of the fiber-softening agent deposited is 0.01 to 50% byweight, preferably 0.1 to 10% by weight, based on the product ofsynthetic fibers to be processed.

The present polycarboxylic acid, the present polyol and other componentscan be deposited on the product of synthetic fibers by variousconventional methods such as dipping, spraying, coating or the like. Inthe practice of the invention, the so-called dipping technique ispreferred in which the product of synthetic fibers to be treated isdipped into a treating solution containing the present polycarboxylicacid, the present polyol and the like. The dipping technique is asdescribed above.

The synthetic fibers are dried after dipping and squeezing. The dryingtemperature is 40° to 150° C. and the drying time is selected accordingto the temperature.

In the invention, subsequently there is heat-treated a product ofsynthetic fibers having the present polycarboxylic acid, the presentpolyol and like components deposited thereon. The heat treatment causesesterification reaction of the present polycarboxylic acid and thepresent polyol sticking to the product of synthetic fibers forconversion into an ester with which the surface of synthetic fiberproduct is coated. If the product of synthetic fibers carries othercomponents than the present polycarboxylic acid and the present polyolas deposited thereon, such as the compound of the formula (4), cationiccellulose and fiber-softening agent, these third components are reactedby heat treatment together with the present polycarboxylic acid and thepresent polyol, whereby a reaction product is produced to cover theproduct of synthetic fibers.

The heat-treating temperature is 100° to 250° C., preferably 120° to200° C. The heat-treating time is 20 seconds to 1 hour. The product ofsynthetic fibers heat-treated under milder conditions is not imparted anenhanced antistatic effect or increased dirt removability, or improvedlaundry durability. Too severe conditions would result in degradedproperties of synthetic fibers, and are likely to decrease the strengthof fibers or to yellow them, hence the conditions outside said rangesare undesirable.

When required, the product of synthetic fibers thus processed is washedwith water, soaped and provided with a fiber-softening agent to give thedesired product. When the product is a filament or thread, it is made bya conventional method into an end product such as textile, knitting,non-woven fabric, clothes, curtains, etc.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is described below in more detail with referenceto the Examples and Test Examples.

EXAMPLE 1

There was prepared an aqueous solution of 4% by weight of1,2,3,4-butanetetracarboxylic acid (hereinafter referred to as "BTC"),8% by weight of "Polyethylene Glycol #600" and 4% by weight ofmonosodium phosphate. A liquid ammonia-treated plain cotton fabric piecewas immersed in the solution at 25° C. for 5 minutes and squeezed at asqueezing ratio of 60%. After drying at 100° C. for 10 minutes, thepiece was heat-treated at 170° C. for 2 minutes, giving a heat-treatedtest fabric sample (processed fabric sample). The processed fabricsample was washed ten times to provide a washed fabric sample.

EXAMPLE 2

There was prepared an aqueous solution of 8% by weight of BTC, 15% byweight of "Polyethylene Glycol #1000", 8% by weight of carboxy-modifiedsilicone, and 4% by weight of sodium malate. Using the solution as atreating solution, the same procedure as in Example 1 was repeated,giving a processed fabric sample and a washed fabric sample.

EXAMPLE 3

There was prepared an aqueous solution of 4% by weight of BTC, 8% byweight of an adduct of 18 moles of ethylene oxide with bisphenol A and0.8% by weight of sodium carbonate. Using the solution as a treatingsolution, the same procedure as in Example 1 was repeated, giving aprocessed fabric sample and a washed fabric sample.

EXAMPLE 4

There was prepared an aqueous solution of 3% by weight of tricarballylicacid, 5% by weight of "Polyethylene Glycol #600" and 4% by weight ofmonosodium phosphate. Using the solution as a treating solution, thesame procedure as in Example 1 was repeated, giving a processed fabricsample and a washed fabric sample.

EXAMPLE 5

There was prepared an aqueous solution of 3% by weight of citric acid,5% by weight of "Polyethylene Glycol #6000" and 4% by weight ofmonosodium phosphate. Using the solution as a treating solution, thesame procedure as in Example 1 was repeated except that heat treatmentwas conducted at 170° C. for 3 minutes, giving a processed fabric sampleand a washed fabric sample.

EXAMPLE 6

There was prepared an aqueous solution of 4% by weight of BTC, 8% byweight of "Polyethylene Glycol #1000", 1% by weight of an adduct of 40moles of ethylene oxide with pentaerythritol, 1% by weight of monosodiumphosphate and 2% by weight of sodium lactate. Using the solution as atreating solution, the same procedure as in Example 1 was repeated,giving a processed fabric sample and a washed fabric sample.

EXAMPLE 7

There was prepared an aqueous solution of 8% by weight of BTC, 15% byweight of "Polyethylene Glycol #1000" and 4% by weight of sodiumhypophosphite. Using the solution as a treating solution, the sameprocedure as in Example 1 was repeated, giving a processed fabric sampleand a washed fabric sample.

EXAMPLE 8

A 4-necked flask reactor equipped with a stirrer was charged with 70 g(0.3 mole) of BTC, 150 g (0.15 mole) of "Polyethylene Glycol #1000" and20 g of water. The temperature was elevated to 150° C. and the reactionsystem was placed under reduced pressure. While eliminating the producedwater, the reaction was continued for 3 hours, giving a viscous liquidof an ester (hereinafter referred to as "ester A"). The ester was foundto have a neutralization value of 246 (mg KOH/g) and an ester value of65 (mg KOH/g).

An aqueous solution of 20% by weight of the above-obtained ester A and4% by weight of sodium hypophosphite was prepared. Using the solution asa treating solution, the same procedure as in Example 1 was repeated,giving a processed fabric sample and a washed fabric sample.

EXAMPLE 9

A 4-necked flask reactor equipped with a stirrer was charged with 23.4 g(0.1 mole) of BTC, 100 g (0.2 mole) of "Polyethylene Glycol #1000" and20 g of water. The temperature was elevated to 150° C. and the reactionsystem was placed under reduced pressure. While eliminating the producedwater, the reaction was continued for 3 hours, giving a viscous liquidof an ester (hereinafter referred to as "ester B"). The ester was foundto have a neutralization value of 104 (mg KOH/g) and an ester value of81 (mg KOH/g).

An aqueous solution of 8% by weight of the above-obtained ester B, 4% byweight of BTC and 3% by weight of sodium lactate was prepared. Using thesolution as a treating solution, the same procedure as in Example 1 wasrepeated, giving a processed fabric sample and a washed fabric sample.

Comparative Example 1

An aqueous solution of 8% by weight of "Polyethylene Glycol #600" and 4%by weight of monosodium phosphate was prepared. Using the solution as atreating solution, the same procedure as in Example 1 was repeated,giving a processed fabric sample and a washed fabric sample.

Comparative Example 2

An aqueous solution of 4% by weight of BTC and 4% by weight ofmonosodium phosphate was prepared. Using the solution as a treatingsolution, the same procedure as in Example 1 was repeated, giving aprocessed fabric sample and a washed fabric sample.

Comparative Example 3

The same procedure as in Example 1 was performed except that heattreatment was not conducted, giving a processed fabric sample and awashed fabric sample.

Comparative Example 4

A plain cotton fabric piece mercerized with an aqueous solution ofsodium hydroxide (namely a plain cotton fabric piece not treated withliquid ammonia) was dipped into the treating solution of Example 1 at25° C. for 5 minutes, and squeezed at a squeezing ratio of 60%. Afterdrying at 100° C. for 10 minutes, the piece was heat-treated at 170° C.for 2 minutes, giving a processed fabric sample. The processed fabricsample was washed ten times to provide a washed fabric sample.

Comparative Example 5

A plain cotton fabric piece was treated with liquid ammonia, giving aprocessed fabric sample which was washed 10 times to provide a washedfabric sample.

Comparative Example 6

A plain cotton fabric piece mercerized with an aqueous solution ofsodium hydroxide was dipped into the treating solution of Example 1 at25° C. for 5 minutes, and squeezed at a squeezing ratio of 60%. Afterdrying at 100° C. for 10 minutes, the piece was heat-treated at 170° C.for 2 minutes and then treated with liquid ammonia, giving a processedfabric sample. The processed fabric sample was washed ten times toprovide a washed fabric sample.

Test Example 1

The washed fabric samples obtained above in Examples 1 to 9 andComparative Examples 1 to 6 were tested as follows.

(1) Dirt removability test

The washed fabric sample was fouled at specified spots with lipstick,soiled motor oil and Indian ink and was left to stand for 2 hours toprovide a fouled fabric sample. Then the fouled fabric sample was washedonce or twice to evaluate the dirt removability according to thefollowing 5-grade rating:

1. No dirt removed

2. Dirt slightly removed

3. Dirt partly removed

4. Dirt markedly removed

5. Only traces of dirt recognizable, or dirt scarcely recognizable.

The results are shown below in Table 1.

                  TABLE 1    ______________________________________    Lipstick       Soiled motor oil                                Indian ink    Washed    Washed   Washed  Washed Washed                                            Washed    once      twice    once    twice  once  twice    ______________________________________    Ex. 1 3       3        4     5      3     4    Ex. 2 3       3        4     5      3     4    Ex. 3 3       3        4     5      3     4    Ex. 4 3       3        3     3      3     4    Ex. 5 3       3        3     3      3     4    Ex. 6 3       3        4     5      3     4    Ex. 7 3       3        4     5      3     4    Ex. 8 3       3        4     5      3     4    Ex. 9 3       3        4     5      3     4    Comp. 1       1        1     1      1     1    Ex. 1    Comp. 1       1        1     1      1     1    Ex. 2    Comp. 1       1        1     1      1     1    Ex. 3    Comp. 1       1        1     1      1     1    Ex. 4    Comp. 1       1        1     1      1     1    Ex. 5    Comp. 1       1        1     1      1     1    Ex. 6    ______________________________________

(2) Antifouling property test

A solution containing 0.3 ml/liter of Indian ink and 2.5 g/liter of ahousehold detergent was prepared and placed into a washing machine. Thewashed fabric sample was washed by the machine to evaluate theantifouling property of the sample according to 5-grade rating by JISdirt grey scale. Grade 1 is the lowest degree of antifouling propertyand Grade 5 is freedom from dirt. The results are shown in Table 2.

                  TABLE 2    ______________________________________           Example 1     Grade 4-5           Example 2     Grade 4-5           Example 3     Grade 4-5           Example 4     Grade 4-5           Example 5     Grade 4-5           Example 6     Grade 4-5           Example 7     Grade 4-5           Comp. Ex. 1   Grade 1           Comp. Ex. 2   Grade 2           Comp. Ex. 3   Grade 1           Comp. Ex. 4   Grade 1           Comp. Ex. 5   Grade 1           Comp. Ex. 6   Grade 1    ______________________________________

EXAMPLE 10

There was prepared an aqueous solution of 4% by weight of BTC, 8% byweight of "Polyethylene Glycol #600" and 4% by weight of monosodiumphosphate. A plain 100% polyester fabric piece was immersed in thissolution at 25° C. for 5 minutes and squeezed at a squeezing ratio of60%. The sample was dried at 100° C. for 10 minutes and heat-treated at180° C. for 3 minutes, giving a heat-treated test fabric sample(processed fabric sample), which was washed ten times to provide awashed fabric sample.

EXAMPLE 11

There was prepared an aqueous solution of 4% by weight of BTC, 10% byweight of "Polyethylene Glycol #1000", 2% by weight of monosodiumphosphate and 2% by weight of sodium hypophosphite. Using the solutionas a treating solution, the same procedure as in Example 10 wasperformed, giving a processed fabric sample and a washed fabric sample.

EXAMPLE 12

There was prepared an aqueous solution of 2% by weight of BTC, 4% byweight of an adduct of 20 moles of ethylene oxide with pentaerythritol,1% by weight of monosodium phosphate and 2% by weight of sodiumhypophosphite. Using the solution as a treating solution, the sameprocedure as in Example 10 was performed, giving a processed fabricsample and a washed fabric sample.

EXAMPLE 13

There was prepared an aqueous solution of 4% by weight of BTC and 8% byweight of an adduct of 18 moles of ethylene oxide with bisphenol A.Using the solution as a treating solution, the same procedure as inExample 10 was performed, giving a processed fabric sample and a washedfabric sample.

EXAMPLE 14

There was prepared an aqueous solution of 3% by weight of BTC, 4% byweight of an adduct of 18 moles of ethylene oxide with bisphenol A, 4%by weight of an adduct of 20 moles of ethylene oxide withethylene-diamine, 1% by weight of monosodium phosphate and 2% by weightof sodium hypophosphite. Using the solution as a treating solution, thesame procedure as in Example 10 was performed, giving a processed fabricsample and a washed fabric sample.

EXAMPLE 15

There was prepared an aqueous solution of 3% by weight of tricarballylicacid, 5% by weight of "Polyethylene Glycol #600" and 4% by weight ofmonosodium phosphate. Using the solution as a treating solution, thesame procedure as in Example 10 was performed, giving a processed fabricsample and a washed fabric sample.

EXAMPLE 16

There was prepared an aqueous solution of 3% by weight of citric acid,5% by weight of "Polyethylene Glycol #6001" and 4% by weight ofmonosodium phosphate. Using the solution as a treating solution, thesame procedure as in Example 10 was performed with the exception ofcarrying out heat treatment at 200° C. for 3 minutes, giving a processedfabric sample and a washed fabric sample.

EXAMPLE 17

There was prepared an aqueous solution of 4% by weight of BTC, 8% byweight of an adduct of 18 moles of ethylene oxide with bisphenol A, 0.3%by weight of sodium isethionate and 4% by weight of sodiumhypophosphite. Using the solution as a treating solution, the sameprocedure as in Example 10 was performed, giving a processed fabricsample and a washed fabric sample.

EXAMPLE 18

There was prepared an aqueous solution of 4% by weight of BTC, 8% byweight of an adduct of 18 moles of ethylene oxide with bisphenol A, 1.0%of lauryl dimethyl (hydroxyethyl) ammonium chloride and 4% by weight ofsodium hypophosphite. Using the solution as a treating solution, thesame procedure as in Example 10 was performed, giving a processed fabricsample and a washed fabric sample.

Comparative Example 7

There was prepared an aqueous solution of 2% by weight of "PolyethyleneGlycol #600" and 4% by weight of monosodium phosphate. Using thesolution as a treating solution, the same procedure as in Example 10 wasperformed, giving a processed fabric sample and a washed fabric sample.

Comparative Example 8

There was prepared an aqueous solution of 4% by weight of BTC and 4% byweight of monosodium phosphate. Using the solution as a treatingsolution, the same procedure as in Example 10 was performed, giving aprocessed fabric sample and a washed fabric sample.

Comparative Example 9

The same procedure as in Example 10 was repeated with the exception ofnot conducting heat treatment, giving a processed fabric sample and awashed fabric sample.

Test Example 2

To evaluate the antistatic property of the processed fabric samples andwashed fabric samples obtained above in Examples 10 to 18 andComparative Examples 7 to 9, the volt (V) of frictional electricity inthe test fabric samples (processed fabric samples and washed fabricsamples) was measured using a Kyo Dai-type frictional electrificationtester. The processed fabric sample obtained in Comparative Example 8was unable to undergo frictional electrification test since a solidsubstance was produced from the sample. The results are shown in Table3.

                  TABLE 3    ______________________________________                 Volt of frictional electricity                 Processed  Washed fabric                 fabric sample                            sample    ______________________________________    Ex. 10        80 V       130 V    Ex. 11        90 V       160 V    Ex. 12       110 V       150 V    Ex. 13       120 V       150 V    Ex. 14        90 V       130 V    Ex. 15       130 V       400 V    Ex. 16       100 V       680 V    Ex. 17        20 V       60 V    Ex. 18        30 V       70 V    Comp.        100 V      5800 V    Ex. 7    Comp.        --         6900 V    Ex. 8    Comp.         70 V      6500 V    Ex. 9    ______________________________________

EXAMPLE 19

There was prepared an aqueous solution of 4% by weight of BTC, 8% byweight of "Polyethylene Glycol #1000", 1% by weight of an adduct of 40moles of ethylene oxide with pentaerythritol, 1% by weight of monosodiumphosphate and 2% by weight of sodium lactate. Using the solution as atreating solution, the same procedure as in Example 10 was repeated fortreatment of a fabric piece made by mix-spinning of polyester and cotton(80/20), giving a processed fabric sample and a washed fabric sample.

EXAMPLE 20

There was prepared an aqueous solution of 4% by weight of BTC, 8% byweight of "Polyethylene Glycol #1000", 1% by weight of an adduct of 40moles of ethylene oxide with pentaerythritol, 1% by weight of monosodiumphosphate, 2% by weight of sodium lactate and 0.3% by weight of sodiumisethionate. Using the solution as a treating solution, the sameprocedure as in Example 19 was performed, giving a processed fabricsample and a washed fabric sample.

Comparative Example 10

An aqueous solution of the same composition as in Example 19 wasprepared with the exception of not using 4% by weight of BTC. Using thesolution as a treating solution, the same procedure as in Example 19 wasperformed, giving a processed fabric sample and a washed fabric sample.

Comparative Example 11

An aqueous solution of the same composition as in Example 19 wasprepared with the exception of not using "Polyethylene Glycol #1000" andthe adduct of 40 moles of ethylene oxide with pentaerythritol. Using thesolution as a treating solution, the same procedure as in Example 19 wasperformed, giving a processed fabric sample and a washed fabric sample.

Test Example 3

To evaluate the antistatic property of the processed fabric samples andwashed fabric samples obtained above in Examples 19 and 20 andComparative Examples 10 and 11, the volt (V) of frictional electricityin the test fabric samples (processed fabric samples and washed fabricsamples) was measured using a rotary static tester of the Kyo DaiChemistry Research Institute type (450 rpm×80 seconds). Table 4 showsthe results of measurement in the atmosphere at a temperature of 20° C.and a relative humidity of 65%. Table 5 shows the results of measurementin the atmosphere at a temperature of 20° C. and a relative humidity of30%.

                  TABLE 4    ______________________________________    Measured at 20° C. and RH of 65%                 Volt of frictional electricity                 Processed  Washed fabric                 fabric sample                            sample    ______________________________________    Ex. 19        80 V       110 V    Ex. 20        20 V       60 V    Comp.         80 V      1800 V    Ex. 10    Comp.        2000 V     1900 V    Ex. 11    ______________________________________

                  TABLE 5    ______________________________________    Measured at 20° C. and RH of 30%                 Volt of frictional electricity                 Processed  Washed fabric                 fabric sample                            sample    ______________________________________    Ex. 19        500 V      900 V    Ex. 20        400 V      800 V    Comp.         900 V     8000 V    Ex. 10    Comp.        3000 V     9700 V    Ex. 11    ______________________________________

EXAMPLE 21

There was prepared an aqueous solution of 8% by weight of BTC, 15% byweight of "Polyethylene Glycol #1000" and 4% by weight of sodium malate.Using the solution as a treating solution, the same procedure as inExample 10 was performed for treatments of a fabric piece made of 100%polyester, a fabric piece made of 80% polyester and 20% cotton or afabric piece made of 50% polyester and 50% cotton, giving a processedfabric sample.

EXAMPLE 22

An aqueous solution of the same composition as in Example 21 wasprepared with the exception of using 8% by weight of sodiumhypophosphite and 0.6% by weight of sodium isethionate in place ofsodium malate. Using the solution as a treating solution, the sameprocedure as in Example 21 was performed, giving a processed fabricsample.

EXAMPLE 23

An aqueous solution of the same composition as in Example 21 wasprepared with the exception of using 6% by weight of monosodiumphosphate and 2% by weight of lauryl dimethyl (hydroxyethyl) ammoniumchloride in place of sodium malate. Using the solution as a treatingsolution, the same procedure as in Example 21 was performed, giving aprocessed fabric sample.

Comparative Example 12

An aqueous solution of the same composition as in Example 21 wasprepared with the exception of not using 8% by weight of BTC. Using thesolution as a treating solution, the same procedure as in Example 21 wasperformed, giving a processed fabric sample.

Comparative Example 13

An aqueous solution of the same composition as in Example 21 wasprepared with the exception of not using 15% by weight of "PolyethyleneGlycol #1000". Using the solution as a treating solution, the sameprocedure as in Example 21 was performed, giving a processed fabricsample.

Test Example 4

The processed fabric samples obtained above in Examples 21 to 23 andComparative Examples 12 and 13 were washed 10 times to provide washedfabric samples, which were tested for the following.

(1) Dirt removability test

The washed samples were fouled at specified spots with lipstick, soiledmotor oil and Indian ink and were left to stand for 2 hours to providefouled fabric samples. Then the fouled fabric samples were washed onceor twice to evaluate the dirt removability according to the following5-grade rating:

1. No dirt removed

2. Dirt slightly removed

3. Dirt markedly removed

4. Only traces of dirt recognizable

5. Dirt scarcely recognizable.

The results are shown below in Tables 6 to 8.

                  TABLE 6    ______________________________________    Fabric made of 100% polyester    Lipstick       Soiled motor oil                                Indian ink    Washed    Washed   Washed  Washed Washed                                            Washed    once      twice    once    twice  once  twice    ______________________________________    Ex.    21    3       3        4     4      4     4    22    3       4        4     5      4     4    23    3       4        4     5      4     4    Comp.    Ex.    12    1       1        1     2      1     2    13    1       1        1     2      1     2    ______________________________________

                  TABLE 7    ______________________________________    Fabric made of 80% polyester and 20% cotton    Lipstick       Soiled motor oil                                Indian ink          Washed  Washed   Washed                                 Washed Washed                                              Washed    Ex.   once    twice    once  twice  once  twice    ______________________________________    21    3       3        4     4      4     4    22    3       4        4     5      4     4    23    3       4        4     5      4     4    Comp.    Ex.    12    1       1        1     2      1     2    13    1       1        1     2      1     2    ______________________________________

                  TABLE 8    ______________________________________    Fabric made of 50% polyester and 50% cotton    Lipstick       Soiled motor oil                                Indian ink          Washed  Washed   Washed                                 Washed Washed                                              Washed    Ex.   once    twice    once  twice  once  twice    ______________________________________    21    3       3        4     4      4     4    22    3       4        4     5      4     4    23    3       4        4     5      4     4    Comp.    Ex.    12    1       1        1     2      1     2    13    1       1        1     2      1     2    ______________________________________

(2) Antifouling property test

A solution containing 0.3 ml/liter of Indian ink and 2.5 g/liter of ahousehold detergent was prepared and placed into a washing machine. Thewashed sample was washed by the machine to evaluate the antifoulingproperty of the sample according to the 5-grade rating by JIS dirt greyscale. Grade 1 was the lowest degree of antifouling property and Grade 5was freedom from dirt.

The results are shown below in Table 9.

                  TABLE 9    ______________________________________                          80% poly-  50% poly-               100%       ester/20%  ester/50%               polyester  cotton     cotton               fabric     fabric     fabric    ______________________________________    Ex. 21     Grade 4-5  Grade 4-5  Grade 4-5    Ex. 22     Grade 4-5  Grade 4-5  Grade 4-5    Ex. 23     Grade 4-5  Grade 4-5  Grade 4-5    Comp.      Grade 2    Grade 1    Grade 1    Ex. 12    Comp.      Grade 2    Grade 1    Grade 1    Ex. 13    ______________________________________

Test Example 5

The washed fabric samples obtained in Examples 10, 17 and 18 andComparative Examples 7 and 8 were used as test fabric samples. Ten ofeach of the test fabric samples were arranged in a row and waterdropswere let fall one by one from a burette onto the test fabric samples toobserve the change on the fabric surface from a mirror-like state to amoisturized state which occurred by absorption of water into the fabric.The results were evaluated according to the following 4-grade rating.The water under JIS K 0050 was used in the test.

1. The waterdrops remained long on the fabric surface.

2. On falling onto the fabric surface, the waterdrops formed a massthereon which remained awhile and was absorbed into the fabric, leavingthe surface moist.

3. On falling onto the fabric surface, the waterdrops formed a mass witha flat, mirror-like surface, which was absorbed into the fabric, leavingthe surface moist.

4. On falling onto the fabric, the waterdrops were immediately absorbedinto the fabric and a mirror-like surface was not observed.

The results are shown below in Table 10. There was no variation in theevaluation value among the 10 fabric samples, namely the same value wasobtained by each group of test fabric samples.

                  TABLE 10    ______________________________________           Ex. 10   Ex. 17  Ex. 18 Comp. Ex. 7                                           Comp. Ex. 8    ______________________________________    Water- 4        4       4      2       2    absorbing    capacity    ______________________________________

We claim:
 1. Liquid ammonia-treated cellulose fibers whose partial orentire exterior is coated with an ester of (A) a polycarboxylic acidhaving at least three carboxyl groups and (B) a hydrophilic polyolhaving an oxyethylene group or groups and at least two alcoholichydroxyl groups and/or which fibers are impregnated with said ester. 2.The cellulose fibers according to claim 1, wherein the polycarboxylicacid is at least one member selected from the group consisting of1,2,3,4-butanetetracarboxylic acid, tricarballylic acid and citric acid.3. The cellulose fibers according to claim 1 or 2, wherein thehydrophilic polyol is at least one member selected from the groupconsisting of polyethylene glycol and an adduct of ethylene oxide. 4.The cellulose fibers according to claim 3, wherein the adduct ofethylene oxide is at least one member selected from the group consistingof an ethylene oxide adduct of bisphenol A, an ethylene oxide adduct ofpentaerythritol and an ethylene oxide adduct of polypropylene glycol. 5.A process for preparing liquid ammonia-treated cellulose fiberscomprising the steps of treating cellulose fibers with liquid ammonia,depositing an ester of (A) a polycarboxylic acid having at least threecarboxyl groups and (B) a hydrophilic polyol having an oxyethylene groupor groups and at least two alcoholic hydroxyl groups on the partial orentire exterior of the liquid ammonia-treated cellulose fibers and/orimpregnating said fibers with said ester, and heating said fibers.
 6. Aprocess for preparing liquid ammonia-treated cellulose fibers comprisingthe steps of treating cellulose fibers with liquid ammonia, depositingpolycarboxylic acid having at least three carboxyl groups andhydrophilic polyol having an oxyethylene group or groups and at leasttwo alcoholic hydroxyl groups on the partial or entire exterior of theliquid ammonia-treated cellulose fibers, and/or impregnating said fiberswith said polycarboxylic acid and said hydrophilic polyol, and heatingsaid fibers.
 7. The process according to claim 5 or 6, wherein thepolycarboxylic acid is at least one member selected from the groupconsisting of 1,2,3,4-butanetetracarboxylic acid, tricarballylic acidand citric acid.
 8. The process according to claim 5 or 6, wherein thehydrophilic polyol is at least one member selected from the groupconsisting of polyethylene glycol and an adduct of ethylene oxide. 9.The process according to claim 8, wherein the adduct of ethylene oxideis at least one member selected from the group consisting of an ethyleneoxide adduct of bisphenol A, an ethylene oxide adduct of pentaerythritoland an ethylene oxide adduct of polypropylene glycol.
 10. A product ofcellulose fibers produced from the cellulose fibers as defined in claim1 or
 2. 11. A product of cellulose fibers produced from the cellulosefibers prepared by the process for preparing cellulose fibers as definedin claim 5 or
 6. 12. A product of cellulose fibers prepared by treatingcellulose fibers with liquid ammonia, making the liquid ammonia-treatedfibers into a product thereof, depositing an ester of (A) apolycarboxylic acid having at least three carboxyl groups and (B) ahydrophilic polyol having an oxyethylene group or groups and at leasttwo alcoholic hydroxyl groups on the partial or entire exterior of theliquid ammonia-treated cellulose fibers, and/or impregnating said fiberswith said ester, and heating said fibers.
 13. A product of cellulosefibers prepared by treating cellulose fibers with liquid ammonia, makingthe liquid ammonia-treated fibers into a product thereof, depositingpolycarboxylic acid having at least three carboxylic groups andhydrophilic polyol having an oxylethylene group or groups and at leasttwo alcoholic hydroxyl groups on the partial or entire exterior of theliquid ammonia-treated cellulose fibers, and/or impregnating said fiberswith said polycarboxylic acid and said hydrophilic polyol, and heatingsaid fibers.